1. Field of the Invention
The present invention relates to covalent bonded nanoporous hybrids and their applications thereof, and, more particularly, to a nanoporous hybrids formed by covalent bonding between a crystalline organic-inorganic hybrid having micropore and gigantic mesoporous materials, containing organic groups on the surface thereof, having a size of 10 nm or more. Since the covalent bonded nanoporous hybrids of the present invention has a large surface area, a multiple pore structure, a large pore volume and includes an organic-inorganic hybrid having backbone flexibility, it can be used as materials for gas storages and liquids, adsorbents, catalysts, membranes, magnetic materials, sensors, photoluminescence, photovoltaic and the like.
2. Description of the Related Art
To date, gigantic mesoporous materials (or mesoporous cellular foams (MCFs)) having mesopores of 10 nm or more have been synthesized using a surfactant and TMB (1,3,5-trimethylbenzene), which is a lipophilic additive, under an acidic condition by an electric heating-type hydrothermal synthesis method [U.S. Pat. No. 6,506,485; J. Am. Chem. Soc., 127, 10794-10795 (2005)]. Recently, attempts to prepare gigantic mesoporous materials under weakly-acidic and neutral conditions of a pH ranging from 4 to 7 by an electric heating method have been made [Small, 1, 744-753 (2005); Chem. Mater., 19, 3041-3051 (2007)]. Further, a method of producing MCF-NH2, which is a gigantic mesoporous material including an organic functional group, by introducing —NH2 group onto the surface of micropores of MCF through covalent bonding between a hydroxy group (—OH) located on the surface of a preformed gigantic mesoporous material and an organic silane, such as aminopropyltriethoxysilane (APTES), was reported [Biosensors and Bioelectronics, 23, 695-700(2007)]. Further, a gigantic mesoporous material of 10 nm or more was produced using both a surfactant and a pore expander during the synthesis of a general mesoporous material, such as MCM-41, SBA-15 or the like.
Meanwhile, a porous organic-inorganic hybrid is defined as a porous organic-inorganic polymeric coordination compound in which a central metal ion is bonded with organic ligands. Further, the porous organic-inorganic hybrid is a crystalline compound having a backbone structure including all organic and inorganic matter and having a molecular sized or nanosized porous structure. The porous organic-inorganic hybrid, which is a term having a wide meaning, is generally referred to as a porous coordination polymer [reference: Angew. Chem. Int. Ed, 43, 2334 (2004)] or a metal-organic framework (MOF) [reference: Chem. Soc. Rev., 32, 276 (2003)]. In particular, since this porous organic-inorganic hybrid has a high surface area and molecular-sized or nanosized pores, the porous organic-inorganic hybrids can be used as adsorbents, gas storage materials, sensors, drug delivery materials, catalysts and catalytic supports, and can also be used to form guest molecules having a size smaller than that of a pore into clathrates or to separate molecules having a size larger than that of a pore. Therefore, recently, research on the porous organic-inorganic hybrid has been actively conducted [Chem. Soc. Rev., 37, 191, (2008)]. In addition to the porous organic-inorganic hybrid, since a nonporous organic-inorganic polymeric coordination compound (or a nonporous organic-inorganic hybrid (NOITH)), such as magnesium tartrate or the like, has unique magnetic and optical properties, research on the nonporous organic-inorganic polymeric coordination compound has been conducted [Science, 318, 58, (2007)].
Methods of producing the gigantic mesoporous material and porous organic-inorganic hybrid and applications thereof have been very well known, but a nanoporous hybrids having the properties of both the gigantic mesoporous material and porous organic-inorganic hybrid has never been reported. Since the gigantic mesoporous material accelerates a diffusion phenomenon due to the large-sized pores thereof and the porous organic-inorganic hybrid has various characteristics, such as ultra-porosity, high surface area, metal framework structure, etc., this novel nanoporous hybrids including the gigantic mesoporous material and porous organic-inorganic hybrid are expected to exhibit new functionalities which have not yet been able to be discovered in the fields of storage materials, adsorbents, catalysts, membranes, and the like, and is expected to bring about the synergistic effects of the two materials.